CN102492295A - Preparation method of ultrafine low precipitation red phosphorus inflaming retarding glass fiber reinforced nylon - Google Patents

Preparation method of ultrafine low precipitation red phosphorus inflaming retarding glass fiber reinforced nylon Download PDF

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Publication number
CN102492295A
CN102492295A CN2011103852508A CN201110385250A CN102492295A CN 102492295 A CN102492295 A CN 102492295A CN 2011103852508 A CN2011103852508 A CN 2011103852508A CN 201110385250 A CN201110385250 A CN 201110385250A CN 102492295 A CN102492295 A CN 102492295A
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red phosphorus
super
temperature
nylon
refinement
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CN102492295B (en
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张明
支长勇
邢强强
韦嘉
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NANJING HONGRUI PLASTIC PRODUCTS CO Ltd
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NANJING HONGRUI PLASTIC PRODUCTS CO Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
    • B29B7/58—Component parts, details or accessories; Auxiliary operations
    • B29B7/72—Measuring, controlling or regulating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/74—Mixing; Kneading using other mixers or combinations of mixers, e.g. of dissimilar mixers ; Plant
    • B29B7/7461—Combinations of dissimilar mixers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/80—Component parts, details or accessories; Auxiliary operations
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
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    • B29B9/00—Making granules
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    • B29B9/14—Making granules characterised by structure or composition fibre-reinforced
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
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    • B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
    • B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
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    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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Abstract

The invention relates to a preparation method of an ultrafine low precipitation red phosphorus inflaming retarding glass fiber reinforced nylon. Raw materials comprise the following substances, by weight: 40-60% of nylon, 10-30% of ultrafine red phosphorus masterbatch, 5-15% of synergistic flame retardant, 5-30% of glass fiber and 1-5% of other auxiliaries. The ultrafine red phosphorus masterbatch is prepared by carrying out liquid nitrogen cryogenic grinding on red phosphorus to have a fineness higher than 1250 mesh; and carrying out melt blending on the red phosphorus, high temperature silicone oil and flexibilizer. The ultrafine low precipitation red phosphorus inflaming retarding glass fiber reinforced nylon is prepared by steps of: weighing the raw materials according to weight percentage; mixing well the raw materials in a high speed mixer; carrying out melt blending in a twin-screw extruder and adding the glass fiber simultaneously; and extruding for granulation. Technological conditions of the extruder are as below: a 1-2 zone temperature of the twin-screw extruder being 230-250 DEG C, a 3-4 zone temperature of 250-270 DEG C, a 5-6 zone temperature of 260-280 DEG C, a 7-8 zone temperature of 240-270 DEG C, a handpiece temperature of 230-250 DEG C and a screw revolving speed of 150-350 round / min.

Description

The low preparation method of red phosphorus flame-retardant glass fiber enhanced nylon that separates out of super-refinement
Technical field
The present invention relates to that a kind of super-refinement is low separates out the preparation method of red phosphorus flame-retardant glass fiber enhanced nylon, can be applicable to fields such as electronic apparatus, automobile engineering, belong to technical field of polymer materials.
Background technology
Red phosphorus flame-retardant glass fiber reinforced nylon material mechanical property is high, good electrical property; And low cigarette, low toxicity when burning can not bring secondary harm to fire fighting, do not contain objectionable impuritiess such as halogen, lead, cadmium, mercury, sexavalent chrome in addition; Meet the RoHS of European Union environmental requirement, be widely used.But red phosphorus is under high temperature, high wet condition; Be oxidized to phosphoric acid especially easily; Again with material in some inorganic minerals generation phosphoric acid salt that reacts, these acid and salt are easy in the polymer materials system phenomenon of acid, a bloom to occur emitting to surface transport; Gently then influence outward appearance, open circuit, equipment can not use, and is heavy then cause electrical equipment puncture, short circuit, cause that entire equipment damages even cause fire.
At present, a main method that solves this type of problem is micro encapsulation to be carried out on the red phosphorus surface handle, isolated moisture, air, the stability of increase red phosphorus.Like patents such as Chinese patent CN1238793N, CN1775664A, CN1632057A, CN8814159A, handle through coating the red phosphorus powder, stablized the performance of red phosphorus.But this stable red phosphorus is in nylon and glass fibre reinforced composite material, and under high temperature, strong shearing action, the capsule layer of red phosphorus inevitably is destroyed or partial destruction, still can deterioration failure.
Chinese patent CN101503568B has introduced the compound coating of organic and inorganic, thermoset coating and thermoplastic covering and usefulness when handling red phosphorus, make coating layer when production is extruded, and plays lubrication, has avoided the destruction of coating layer as far as possible.Chinese patent CN101684196A uses ammonium sulfate as initiator, and the preparation point of ignition surpasses 450 ℃ micro encapsulation red phosphorus, and with modified layered pair of Ripon powder as synergistic flame retardant.
Solving red phosphorus, to separate out another method of Problem of Failure be in matrix material, to add acid absorber or unicorn is separated out stablizer, and the phosphorus substance of separating out is on a small quantity neutralized.Adopted examples of such additives exactly like Chinese patent CN101619166B and CN102115595A, to reduce separating out of red phosphorus.
The size of the above all not mentioned red phosphorus powder of patent documentation is for the influence of separating out.The particle diameter of micro encapsulation red phosphorus powder in the market is generally the 100-800 order.
Summary of the invention
The present invention proposes the low preparation method of red phosphorus glass fiber enhanced nylon that separates out of a kind of super-refinement.This method is pulverized the method for red phosphorus through liquid nitrogen freezing, and the red phosphorus particle diameter is refine to more than 1250 orders, is reduced under high temperature, the strong shearing action destruction to red phosphorus.Utilize high-temperature silicon oil and toughner double-coated red phosphorus surface simultaneously, play protection red phosphorus and the effect that increases the red phosphorus consistency.
The present invention adopts following technical scheme:
After nylon, super-refinement red phosphorus master batch, synergistic flame retardant, other auxiliary agents were mixed, melt blending in twin screw extruder added spun glass, extruding pelletization simultaneously; The forcing machine processing condition are: twin screw extruder 1-2 district temperature is 230-250 ℃; 3-4 district temperature is 250-270 ℃, and 5-6 district temperature is 260-280 ℃, and 7-8 district temperature is 240-270 ℃; Head temperature is 230-250 ℃, and screw speed is 150-350 rev/min;
Above-mentioned each raw material consumption by weight percentage is following:
Nylon 40～60%,
Super-refinement red phosphorus master batch 10～30%,
Synergistic flame retardant 5～15%,
Spun glass 5～30%
Other auxiliary agents 1～5%
Above-mentioned super-refinement red phosphorus master batch prepares process and is:
1) red phosphorus is pulverized 1250 order calibration sieve through liquid nitrogen freezing, obtained the super-refinement red phosphorus of particle diameter more than 1250 orders;
2) super-refinement red phosphorus and high-temperature silicon oil are mixed, the consumption of aforementioned high-temperature silicon oil is 1～5% of a super-refinement red phosphorus weight;
3) will be through step 2) super-refinement red phosphorus and the toughner blend granulation on forcing machine handled; The consumption of toughner is 30～70% of a super-refinement red phosphorus master batch weight, and the forcing machine processing condition are: twin screw extruder 1-2 district temperature is 160-190 ℃, and 3-4 district temperature is 200-220 ℃; 5-6 district temperature is 210-230 ℃; 7-8 district temperature is 210-230 ℃, and head temperature is 170-190 ℃, and screw speed is 150-300 rev/min.
Above-mentioned nylon is the mixture of nylon 66, nylon 6 or both arbitrary proportions, and viscosity is at 2.4-2.7.
Above-mentioned synergistic flame retardant is Marinco H or aluminium-hydroxide powder, and fineness is 400～800 orders, is beneficial to disperse;
Above-mentioned alkali-free continuous glass fibre, filament diameter with maintenance intensity, and are beneficial to smooth surface at 8～18 μ m;
Above-mentioned red phosphorus is commercially available, and its particle diameter is usually at the 100-800 order,
Why the particle diameter of above-mentioned ultra-fine red phosphorus requires more than 1250 orders, is in order in subsequent handling, to be reduced under high temperature, the strong shearing action destruction to red phosphorus.
Above-mentioned high-temperature silicon oil is preferably boiling point at the silicone oil more than 400 ℃, to guarantee that when the high temperature process, silicone oil is non-volatile, plays the protection lubrication.
Above-mentioned toughner is SBS or SEBS through maleic anhydride, glycidyl acrylate graft modification; Melting index is 0.5-10g/10min; Percentage of grafting is 0.3%-1.5%; Its reason is that the applicant finds after deliberation, if melting index can cause processing difficulties not in the 0.5-10g/10min scope; And percentage of grafting is in the 0.3%-1.5% scope, and toughening effect is best, crosses that low then toughening effect is not obvious, and too high then material has tangible irritating smell.
Other above-mentioned auxiliary agents are conventional oxidation inhibitor and lubricant, and both concrete consumptions do not have special requirement, and its total amount control gets final product 11～5%.Preferred 1010,168 mixtures in 1: 1 ratio of oxidation inhibitor wherein, lubricant preferably selects calcium stearate, Zinic stearas, EBS or polyethylene wax.
The super-refinement that adopts the present invention to make is low separates out the red phosphorus flame-retardant glass fiber enhanced nylon when having guaranteed material mechanical performance and flame retardant resistance, and the phosphorus amount of separating out is minimum to be 25ppm, can match in excellence or beauty with the phosphorus amount of separating out of German BASF like product.
Specific embodiments
Following examples are in order to further explanation the present invention, but the present invention is not only limited to these embodiment.
One, the preparation of super-refinement red phosphorus master batch
The red phosphorus of particle diameter more than 1250 orders of pulverizing through liquid nitrogen mixes with 1% high-temperature silicon oil, and with maleic anhydride graft SBS extruding pelletization in forcing machine, toughner content is 70% in the master batch again, is super-refinement red phosphorus master batch A.
The red phosphorus of particle diameter more than 1250 orders of pulverizing through liquid nitrogen mixes with 3% high-temperature silicon oil, and with maleic anhydride graft SEBS extruding pelletization in forcing machine, toughner content is 50% in the master batch again, is super-refinement red phosphorus mother particle B.
The red phosphorus of particle diameter more than 1250 orders of pulverizing through liquid nitrogen mixes with 5% high-temperature silicon oil, and with glycidyl acrylate SBS extruding pelletization in forcing machine, toughner content is 30% in the master batch again, is super-refinement red phosphorus master batch C.
The red phosphorus of particle diameter more than 1250 orders of pulverizing through liquid nitrogen mixes with 5% high-temperature silicon oil, and with glycidyl acrylate SEBS extruding pelletization in forcing machine, toughner content is 30% in the master batch again, is super-refinement red phosphorus master batch D.
Two, each component is mixed in high-speed mixer by listed formula ratio in the table 1, melt blending in twin screw extruder adds spun glass, extruding pelletization simultaneously.The forcing machine processing condition are: twin screw extruder 1-2 district temperature is 230-250 ℃; 3-4 district temperature is 250-270 ℃, and 5-6 district temperature is 260-280 ℃, and 7-8 district temperature is 240-270 ℃; Head temperature is 230-250 ℃, and screw speed is 150-350 rev/min.
The gained material makes batten 110 ℃ of dryings 4 hours through injection moulding, presses ISO and UL standard testing performance, and the result sees table 2.
Embodiment 1,2,3,4 and Comparative Examples 1,2 prescriptions (table 1)
Figure BDA0000113501380000041
Embodiment 1,2,3,4 and Comparative Examples 1,2 performance synopsis (table 2)
Test event Comparative Examples 1 Comparative Examples 2 Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4
Tensile strength (MPa) 101 115 70 97 128 120
Flexural strength (MPa) 142 159 91 136 172 155
Modulus in flexure (MPa) 5223 6028 3964 4902 8013 6207
Notched Izod impact strength (KJ/m 2) 6.2 7.7 12.6 11.9 9.5 9.1
Flame retardant resistance (3.2mm) V-0 V-0 V-0 V-0 V-0 V-0
The phosphorus amount of separating out (ppm) 1025 886 75 122 96 25

Claims (8)

1. a super-refinement hangs down and separates out the preparation method of red phosphorus flame-retardant glass fiber enhanced nylon, it is characterized in that
After nylon, super-refinement red phosphorus master batch, synergistic flame retardant, other auxiliary agents were mixed, melt blending in twin screw extruder added spun glass, extruding pelletization simultaneously; The forcing machine processing condition are: twin screw extruder 1-2 district temperature is 230-250 ℃; 3-4 district temperature is 250-270 ℃, and 5-6 district temperature is 260-280 ℃, and 7-8 district temperature is 240-270 ℃; Head temperature is 230-250 ℃, and screw speed is 150-350 rev/min;
Above-mentioned each raw material consumption by weight percentage is following:
Nylon 40～60%,
Super-refinement red phosphorus master batch 10～30%,
Synergistic flame retardant 5～15%,
Spun glass 5～30%
Other auxiliary agents 1～5%
Above-mentioned super-refinement red phosphorus master batch prepares process and is:
1) red phosphorus is pulverized 1250 order calibration sieve through liquid nitrogen freezing, obtained the super-refinement red phosphorus of particle diameter more than 1250 orders;
2) super-refinement red phosphorus and high-temperature silicon oil are mixed, the consumption of aforementioned high-temperature silicon oil is 1～5% of a super-refinement red phosphorus weight;
3) will be through step 2) super-refinement red phosphorus and the toughner blend granulation on forcing machine handled; The consumption of toughner is 30～70% of a super-refinement red phosphorus master batch weight, and the forcing machine processing condition are: twin screw extruder 1-2 district temperature is 160-190 ℃, and 3-4 district temperature is 200-220 ℃; 5-6 district temperature is 210-230 ℃; 7-8 district temperature is 210-230 ℃, and head temperature is 170-190 ℃, and screw speed is 150-300 rev/min.
2. by the described method of claim 1, it is characterized in that nylon is the mixture of nylon 66, nylon 6 or both arbitrary proportions, viscosity is at 2.4-2.7.
3. by the described method of claim 1, it is characterized in that synergistic flame retardant is Marinco H or aluminium-hydroxide powder, granularity is 400～800 orders.
4. by the described method of claim 1, it is characterized in that spun glass is the alkali-free continuous glass fibre, filament diameter is at 8～18 μ m.
5. by the described method of claim 1, the particle diameter that it is characterized in that red phosphorus is at the 100-800 order.
6. by the said method of claim 1, it is characterized in that high-temperature silicon oil is that boiling point is at the silicone oil more than 400 ℃.
7. by the described method of claim 1, it is characterized in that toughner is that melting index is 0.5-10g/10min through the SBS or the SEBS of maleic anhydride, glycidyl acrylate graft modification, percentage of grafting is 0.3%-1.5%.
8. by the described method of claim 1, it is characterized in that other auxiliary agents are the mixture of oxidation inhibitor, lubricant.
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CN105220268A (en) * 2015-09-15 2016-01-06 郎溪和心化纤织造有限公司 A kind of POLYAMIDE YARNS with high efficiency flame retardance
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CN103642223A (en) * 2013-11-18 2014-03-19 安徽宜万丰电器有限公司 Anti-ultraviolet ageing-resistant modified nylon 66 material for automobile plastic members
CN105220268A (en) * 2015-09-15 2016-01-06 郎溪和心化纤织造有限公司 A kind of POLYAMIDE YARNS with high efficiency flame retardance
CN107254167A (en) * 2017-06-09 2017-10-17 江苏特耐奇工程塑业有限公司 Corrosion-resistant fire-retardant nylon material
CN108178883A (en) * 2018-02-01 2018-06-19 哈尔滨理工大学 A kind of halogen-free flameproof polystyrene of fire retardant selective distribution and preparation method thereof
CN110564147A (en) * 2018-06-05 2019-12-13 中蓝晨光化工研究设计院有限公司 High-oxygen-index red phosphorus flame-retardant reinforced nylon 66 compound and preparation method thereof
CN110564147B (en) * 2018-06-05 2022-03-25 中蓝晨光化工研究设计院有限公司 High-oxygen-index red phosphorus flame-retardant reinforced nylon 66 compound and preparation method thereof
CN109679338A (en) * 2018-12-23 2019-04-26 德力西电气有限公司 A kind of halogen-free flame-retardant polyamide alloy material of low precipitation and preparation method thereof
CN111117222A (en) * 2019-12-12 2020-05-08 中广核俊尔(浙江)新材料有限公司 Glow-wire-resistant nonflammable polyamide composition and preparation method and application thereof
CN111117222B (en) * 2019-12-12 2022-03-15 中广核俊尔(浙江)新材料有限公司 Glow-wire-resistant nonflammable polyamide composition and preparation method and application thereof
CN114672160A (en) * 2022-03-17 2022-06-28 金发科技股份有限公司 High-tracking-resistance red phosphorus flame-retardant polyamide composition and preparation method and application thereof
CN114672160B (en) * 2022-03-17 2023-11-21 金发科技股份有限公司 Red phosphorus flame-retardant polyamide composition with high tracking resistance, and preparation method and application thereof

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